CH.6.

GALVANIC CORROSION

Why yg galvanic corrosion

Happens when two dissimilar metals are connected In the couple, couple the less noble of the two metals corroding more rapidly, while the more noble corrodes less. The driving force: a potential difference between two metals

Galvanic Corrosion (Dissimilar Metal Corrosion)

A potential difference exists between two dissimilar metals connected electrically a current will flow between them corrosion rate of less resistance metal (anodic) .
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Galvanic series in seawater

Kinetics of a Zn/Pt Galvanic Couple p

io,H2(Zn)=10-10 A/cm2 io,H2(Pt)=10 10-3 A/cm2

e-

Zn

Zn2+

Pt H2

Galvanic coupling Zn to Pt; Shifts the corrosion potential of Zn from Ecorr to Ecouple Increases I th the corrosion i rate t f from icorr(Zn) to t icorr(Zn-Pt) Decreases the hydrogen evolution rate on Zn form iH2(Zn) to iH2(Zn-Pt)
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Effect of Exchange Current Density by Comparison of ZnZn - Pt and ZnZn - Au Couples

EAu3+/Au = 1.498 V io,H2(Au) = 10-6 A/cm2 EPt2+/Pt = 1.2 V io,H2(Pt) = 10-3 A/cm2 icorr(Zn-Pt) > icorr(Zn-Au) > icorr(Zn) Ecorr(Zn-Pt) > Ecorr(Zn-Au) The reason why gold produces a less severe galvanic effect is not related to its reversible potential but rather to the fact that it has a lower hydrogen exchange current density than platinum.

Effect of Area Ratio

Corrosion of Galvanic Couple between Two Metals

Zn-Fe couple in a deaerated solution
ErH /H
+

io,H /H
+ 2

(Zn)

io,H /H
+

(Fe)

FeFe2+ +2eZnZn2+ +2e 2e-

icorr(Fe) Er,Fe icorr(Fe - Zn) io,Fe F Er,Zn

10-10 10-8
2+

icorr(Fe - Zn)

icouple icorr(Zn)

/F /Fe

io,Zn

2+

/Zn 10-6 10-4 10-2 10-0 log |i|

General Conclusions on Galvanic Corrosion

If two corroding metals are galvanically coupled, the corrosion rate of more active potential (i.e., with more active corrosion potential) is accelerated, and that of the other metal is retarded. The polarity of electrode for galvanic couple should be defined on the t e bas basis so of co corrosion os o pote potential, t a , not ot o on co corrosion os o rate. ate The corrosion behavior of a galvanic couple is determined by the following parameters : Er, io, and the relative areas of the two metals. Galvanic corrosion behavior can not be predicted accurately on the basis of EMF series. Use galvanic series to predict corrosion behavior of g galvanic couple. p

Corrosion of Galvanic Couple Containing ActiveActive - Passive Metal

Case 1: Epp < EH+/H2, e.g., Ti-Pt, Cr-Pt in acid solution

Coupling of Ti to Pt leads to spontaneous passivation of Ti without

oxidizers.

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Development of corrosion resistant alloy based on galvanic corrosion [Noble metal alloying] Alloying of Ti or Cr with a noble metal such as Pt Pt, Pd Pd, Rh and Ir with low hydrogen overvoltage produces spontaneous passivation in hot concentrated oxidizer-free acid. Homogeneous solution of Pt in Ti Preferential dissolution of Ti Enrichment of Pt on surface of alloy Spontaneous passivation

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Corrosion of Galvanic Couple Containing ActiveActive - Passive Metal

Case 2: Epp > EH+/H2, e.g., Fe-Pt couple in acid solution

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Galvanic Corrosion Area Effect

The localized pinhole corrosion has developed through the coating. ti All coatings have defects in the form of p pinholes and mechanical damage. Anodic dissolution and galvanic corrosion of the carbon steel were concentrated at coating defects by a large cathode (stainless steel)/anode (steel) surface area ratio ratio.

Coating

Carbon steel

Localized corrosion occurred Weldment

18-8 stainless steel

Painted steel storage tank Figure 6.2

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Corrosion in a Weld
How to Select an Optimum Filler Metal Welding of stainless steel can cause sensitization and hence intergranular corrosion in heat affected zone (HAZ) As a filler metal, Select more resistive one to corrosion than base metal. (i.e., With higher Ecorr) (Small cathode large anode)

filler metal fill t l 308L SS (20Cr-11Ni) 347 SS (18Cr-11Ni-Nb)

base metal 304L SS (18Cr-8Ni)

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Prevention against g Galvanic Corrosion

1) 2) 3) 4) 5) 6) Select combinations of metals as close together as possible in the galvanic series. Avoid the unfavorable effect of a small anode and large cathode Insulate the components from each other. other Apply coatings with caution. Add inhibitors into solution. Install a third metal that is anodic to both metal in the galvanic series.

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Differential Aeration Cell (Oxygen Concentration Cell)

The concentration of oxygen dissolved in water or soil frequently varies from one point to another. This difference in aeration produces a different equilibrium potential. For the oxygen reduction reaction in water

1/2 O2 + 2H+ + 2e- H2O eO = e + 0.059/2 log (aO )1/2 (aH+)2/ (aH O)
2 2 2

Thus, a stronger oxygen conc. provides a more noble equilibrium potential. Chemical reaction in low O2 compartment:

A Anodic di dissolution di l ti : Fe F Fe F 2+ + 2e 2 Hydrolysis reaction : Fe2+ + 2H2O Fe(OH)2 + 2H+ pH . Low pH prevent passivation and undergoes severe corrosion Oxygen reduction : O2 + 2H2O + 4e- 4OH- pH High pH favors the formation of passive film

Chemical reaction in High O2 compartment

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Corrosion of Fe in Differential Aeration Cell

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Differential Aeration ( (cont.) )

water-line corrosion ( (Fig. g 6.26 ) )

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Reference

KAIST , http://corrosion.kaist.ac.kr

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Homework

Problems 3, 4, 6 of Chapter 6 in the textbook.

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